The Scotsman was one of the stars of the Games four years ago as he claimed golds in the Sprint, Team Sprint and his favoured Keirin event to add to his time-trial triumph at Athens 2004.
Hoy, Jason Kenny and Philip Hindes will have the backing of a partisan home crowd when they compete in the Team Sprint and a fifth gold medal will ensure legend status for Hoy.
Great Britain are the Olympic Games champions, but Germany, France, Australia and New Zealand are also expected to contest the medals.
Australia, Germany and Great Britain are expected to be the leading contenders for medals in the women’s Team Sprint.
At the Aquatics Centre, Michael Phelps has an opportunity to take his record-breaking Olympic medal tally to 20 when he defends his 200m Individual Medley title but fellow American Ryan Lochte will fancy his chances after winning gold over the 400m distance.
Lochte also has high hopes of winning a gold medal in the final of the 200m Backstroke.
The Netherlands' Ranomi Kromowidjojo, China’s Yi Tang and Melanie Schlanger of Australia are expected to challenge for medals in the women’s 100m Freestyle, while home hopes rest with Fran Halsall.
Rebecca Soni will try to defend the women’s 200m Breaststroke title she won in Beijing and the 25-year-old from New Jersey is a strong favourite to win another gold.
There is also another thrilling day in prospect at Eton Dorney, with Rowing medals up for grabs in the women’s Eight, the men’s Lightweight Fours and the men’s Double Sculls.
More Gymnastics drama is in store at the North Greenwich Arena for the women’s Individual All-Around final, with Russia’s Viktoria Komova and the USA’s Gabby Douglas among the favourites for gold.
Day 6 will also feature the men’s Singles Table Tennis final at ExCeL and there will be Shooting gold at stake in the men’s Double Trap final at the Royal Artillery Barracks.
At the Lee Valley White Water Centre, the final of men's Canoe Double (C2) and the women's Kayak (K1) takes place in the afternoon.
Judo medals will be contested in the men's Half-Heavyweight (90-100kg) and the women’s Half-Heavyweight (70-78kg), while Olympic champions will also be crowned in women’s Team Foil Fencing and women’s Individual Archery.